CN104781307B - Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof - Google Patents

Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof Download PDF

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Publication number
CN104781307B
CN104781307B CN201380058014.2A CN201380058014A CN104781307B CN 104781307 B CN104781307 B CN 104781307B CN 201380058014 A CN201380058014 A CN 201380058014A CN 104781307 B CN104781307 B CN 104781307B
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resin
phenylene ether
epoxy resin
polynary
phenol
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CN104781307A (en
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中西政隆
井上真
井上一真
长谷川笃彦
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyethers (AREA)

Abstract

The objective of the present invention is to provide: a polyvalent phenylene ether novolac resin that provides a cured product having high heat resistance and superior dielectric properties; and an epoxy resin composition containing same. In the polyvalent phenylene ether novolac resin, a poly(phenylene ether) resin having a molecular weight of 400-8000 (weight average molecular weight; in terms of polystyrene) is bonded by means of an organic group.

Description

Polynary phenylene ether novolac resin, composition epoxy resin and its solidfied material
Technical field
The present invention relates to be suitable for requirement thermostability, the phenol of the electric and electronic material applications of electrical characteristic (dielectric property etc.) Novolac resin, composition epoxy resin and its solidfied material.
Background technology
Composition epoxy resin is due to the excellent electrical characteristic of operability and its solidfied material, thermostability, adhesivity, moisture-proof Property (resistance to water) etc. and be widely used in the fields such as electrical and electronic parts, structure material material, adhesive, coating.
But, in recent years, in electric and electronic field, with the development in the field, it is desirable to further improve with resin group Moisture-proof, adaptation, dielectric property headed by the high purity of compound, for making filler (inorganic or organic filler) highly fill out The lowering viscousity that fills, for shortening each characteristic such as the raising reactivity of molding cycle.In addition, as structural material, navigating in aviation The material of light weight and good mechanical performance is required in its material, outdoor activity apparatus purposes etc..
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2003-12796 publications
Patent documentation 2：Japanese Unexamined Patent Publication 2006-291178 publications
The content of the invention
Invent problem to be solved
In encapsulating semiconductor field, with the transition of the quasiconductor, substrate (substrate itself or its periphery material) is gradually thin Stratification, stacked, systematization, three dimensional stress and complicate, it is desirable to the desirable characteristics such as very high-caliber thermostability, high fluidity. Additionally, in order to realize high-speed communication, requiring excellent dielectric property to quasiconductor periphery material.During the dielectric property difference, due to Produce delay, the noise of the signal of telecommunication, it is difficult to realize the high speed of the signal of telecommunication.
In such field, especially for the network substrate of server etc. for, it is desirable to dielectric in high frequency is special Property.For the network environment of constant evolution year by year, low-dielectric loss angle tangent in dielectric property, is the particularly important is.At this Polyphenylene oxide resin is in most cases mainly used in planting purposes, various researchs have been carried out.
Polyphenylene oxide resin is characterised by its very excellent dielectric property, but in order to embody its dielectric property, functional group Seldom, its thermostability is low becomes problem.
According to report in recent years, for such problem, the methods (a) such as introducing functional group carried out, or be set to double officials Can the research such as (b), (a) in be difficult to introduce functional group, thus almost do not obtain practical, though have some to change in (b) It is kind, but still be inadequate level.
In the face of such problem, we complete the present invention.
That is, it is an object of the invention to provide polynary phenylene ether novolac resin, containing the polynary phenylene ether phenol The composition epoxy resin and its solidfied material of Novolac resin, the polynary phenylene ether novolac resin can be provided in holding The solidfied material of excellent heat resistance while excellent dielectric property.
Means for solving the problem
As a result the present inventor completes the present invention in view of above-mentioned present situation, has made intensive studies.
That is, the present invention is provided：
[1] a kind of polynary phenylene ether novolac resin, which passes through (weight average molecular weight, to press molecular weight 400～8000 Polystyrene conversion) polyphenylene oxide resin by organic group connect and obtain；
[2] the polynary phenylene ether novolac resin as described in [1], wherein, organic group by following formula (1) extremely A kind of few expression；
(in formula, * parts are bonded with the benzene skeleton of polyphenylene oxide resin.)
[3] the polynary phenylene ether novolac resin as described in [1] or [2], wherein, the polyphenylene oxide described in [1] or [2] Resin is the oxypolymer of biphenyl phenols or bisphenols and Phenol compounds；
[4] a kind of composition epoxy resin, which contains polynary any one of at least one above-mentioned item [1]～[3] Phenylene ether novolac resin；
[5] a kind of solidfied material, which is obtained by making the epoxy resin composition described in above-mentioned item [4].
Invention effect
Not only had using the solidfied material of the composition epoxy resin of the polynary phenylene ether novolac resin of the present invention High dielectric property, and excellent thermostability is shown, with electrical and electronic parts insulant and plywood (printed wiring Plate, increasing layer substrate etc.), it is the various composites headed by CFRP, adhesive, useful in coating etc..Especially as protection quasiconductor The semiconductor-encapsulating material of element is extremely useful.
Specific embodiment
The polynary phenylene ether novolac resin of the present invention has the resin of polyphenyl ether structure organic by alkylidene etc. The structure that group (also referred to as binding groups or linking group below) is bonded.That is, polynary phenylene ether novolaks of the invention Resin is the resin of the structure of the resin with polyphenyl ether structure and novolac resin.
The resin of polyphenyl ether structure specifically refers to the resin described in above-mentioned patent documentation 1, patent documentation 2, usually diformazan The oxypolymer of base phenol or pseudocuminol, but it is also possible to enumerate xenol the resin as described in patent documentation 2 Oxypolymer of Phenol compounds such as class or bisphenols and 2,6- xylenols etc..
Here, as bisphenols, it is possible to use such as bisphenols such as bisphenol-A, Bisphenol F, bisphenol S, bis-phenol I.As commercially available Product, can enumerate the PPO (registered trade mark) of SABIC, especially consider from the scope of molecular weight, preferred SA120, SA90-100 Deng.In addition, especially considering from multiple functionalized degree, difunctional material as SA90-100 is preferably used.As biphenyl Phenols, can enumerate the compound of such as following formula.
(in formula, R1Each independent substituent group is represented, is hydrogen atom, halogen atom, the alkyl of carbon number 1～3, virtue Alkyl, aryl, alkoxyl, t represent 1～4 integer.)
As Phenol compounds, orthoresol, 2,6- xylenols, 2,3,6-TMP, 2- ethyls can be enumerated Phenol, 2- methyl -6- ethyl -phenols, 2,6- diethyl phenols, 2- n-pro-pyl phenol, 2- ethyl -6- n-pro-pyl phenol, 2- first Base -6- chlorophenols, 2- methyl -6- bromophenols, 2- methyl -6- isopropyl-phenols, 2- methyl -6- n-pro-pyl phenol, 2- ethyl -6- Bromophenol, 2- methyl -6- normal-butyl phenol, 2,6- diη-propyl phenol, 2- ethyl -6- chlorophenols, 2- methyl -6- phenyl benzene Phenol, 2- phenylphenols, 2,6- diphenyl phenol, 2,6- double (4- fluorophenyls) phenol, 2- methyl -6- tolyl phenol, 2,6- bis- The unitary phenolic compounds such as tolyl phenol.
The molecular weight of the polyphenylene oxide resin for using be 400～8000 (weight average molecular weight, gel permeation chromatography, by polyphenyl second Alkene convert), be preferably 500～4000.
When the molecular weight of the resin for using is too high, to the compatibility in a solvent and the compatibility of other resins in terms of make Into obstacle, occur to separate when including solidfied material, cause to solidify the skewness of bad, characteristic, thus it is not preferred.In addition, point Son amount hour, when especially about 200, does not show the difference of larger dielectric property compared with conventional novolac resin, Therefore it is not preferred.
As the control of these molecular weight, not only connected by merely making molecule, it is also possible to which enumerating can be by being based on The depolymerization of free radical is controlling the example of molecular weight.
In the polynary phenylene ether novolac resin of the present invention, connect phenylene structure by binding groups, be consequently formed The form (for convenience's sake, being all expressed as novolaks) of novolaks or similar novolaks.
Used as binding groups, preferred carbon number is 1～20 alkyl.Methylene, ethylidene, Asia third can specifically be enumerated Base, hexamethylene diyl, phenylmethylene, phenylene dimethylene, ethenylidene dimethylene, phenylene acetylene, sub- benzene Double propylidene of base etc..
As the binding groups in the present invention, the structure shown in particularly preferred following formula (1).
(in formula, * parts are bonded with the benzene skeleton of polyphenylene oxide resin.)
As the bonding method of these linking groups, it is possible to use raw material polyphenylene oxide resin and various aldehydes, ketone, benzyl Methylene compound, the compound with vinyl benzene structure etc. into key compound, in the presence of solvent in acid or alkaline bar Heat to synthesize under part.
Here, as the concrete example into key compound, formaldehyde, acetaldehyde, Biformyl, propionic aldehyde, isovaleral, pungent can be enumerated The aldehydes such as aldehyde, furfural, benzaldehyde, pyridine carboxaldehyde；The ketones such as acetone, butanone, Ketocyclopentane, Ketohexamethylene；Benzene dimethanol, dihalo Dimethylbenzene (halogen：Chlorine, bromine etc. can be enumerated), bis-alkoxy methylbenzene (xylylene double alkyl ether, be specially bi-methoxy Methylbenzene, double ethoxyl methyl benzene, double propoxy methyl benzene, Ramulus Uncariae Cum Uncis epoxide methylbenzene, double phenoxymethyl benzene, diene propoxyl group Alkoxy methyl benzene of the carbon numbers such as methylbenzene 1～6 etc..Particularly preferred benzene dimethanol in this synthetic reaction, xylene dichloride, Bi-methoxy methylbenzene.It should be noted that the configuration of substituent group can be it is o-, m-, centering any one, from thermostability, machine The balance of tool characteristic considers, particularly preferably to formula.) etc. xylylene compounds；Biphenyl dimethanol, double halogenated methyl biphenyl (halogen：Chlorine, bromine etc. can be enumerated), bis-alkoxy methyl biphenyl (specially bi-methoxy methyl biphenyl, double ethoxyl methyls connection The carbon such as benzene, double propoxy methyl biphenyl, Ramulus Uncariae Cum Uncis epoxide methyl biphenyl, double phenoxymethyl biphenyl, bisallyloxylmethyl biphenyl Alkoxy methyl biphenyl of atomic number 1～6 etc.) etc. benzyl methylene compound, the divinyl such as biphenyl bismethylene compound class The compound with vinyl benzene structure such as base benzene.
In this synthetic reaction, particularly preferred biphenyl dimethanol, dichloride methyl biphenyl, bi-methoxy methyl biphenyl.
The polynary phenylene ether novolac resin of the present invention can be by by raw material polyphenylene oxide resin and into key compound Heated after catalyst being added as needed in the mixed liquor of solvent and obtained.
Alternatively, it is also possible to be slowly added into in the solution of raw material polyphenylene oxide resin and catalyst as needed is dissolved with Key compound.Response time is usually 3～150 hours, usually 40～150 DEG C of reaction temperature.So obtained polynary sub- benzene Base ether novolac resin can also be used in the case of unpurified according to purposes, but generally after the completion of reaction as needed Reactant mixture is neutralized etc. and to be processed, then by crystallization or solvent is removed under heating decompression and carried out after purification For various uses.Further, since the mean molecule quantity of the polynary phenylene ether novolac resin obtained by reacting and making increases Greatly, therefore the softening point of resin becomes very high, it is difficult to take out from reaction vessel, thus can utilize following (a)～(d's) Method.
A () is by using water-soluble solvent dilution after, mixes with water.
B () is diluted by using the alcohols (methanol, ethanol, propanol, butanol etc.) that carbon number is 1～4, and carry out Method obtained from reprecipitation.
C water (heating decompression etc.) that () is contained in only removing the solvent after reaction purification terminates, then with solvent cut The method that the form of the varnish of (molten drug カ ッ ト) is taken out from reaction vessel.(as resin concentration, preferably 10～90 weights Amount %, more preferably 10～80 weight %, particularly preferably 30～80 weight %).In most cases especially pay attention to viscosity, from which From the aspect of mobility, the viscosity at 25 DEG C is preferably below 1000Pas, more preferably below 100Pas.Viscosity is too high When, no mobility when in use, thus be difficult to sometimes take out or be difficult to and other mixed with resin.It should be noted that closing Be described below in the solvent that can be used (be hardening resin composition varnish item described in solvent).
D () is mixed with other resins (resin described in the item of hardening resin composition firming agent described later), with The method that the form of curing agent composition is taken out from reaction vessel.(mixed proportion is with other resins and the resin of the present invention Weight ratio meter is preferably 90：10～30：70th, more preferably 80：20～30：70.When the use level of the resin of the present invention is few, dielectric Characteristic is not greatly improved.)
In addition, raw material polyphenylene oxide resin is preferably 1.2 with the reaction mol ratio (hydroxyl equivalent ratio) into key compound：1～ 20：1st, more preferably 1.5：1～15：1st, particularly preferably 1.5：1～10：1.Reaction mol ratio is less than 1.2：When 1, i.e., relative to Into key compound 1, when raw material polyphenylene oxide resin is less than 1.2, the molecule quantitative change of the polynary phenylene ether novolac resin of generation It is too much, therefore dissolubility in a solvent and be deteriorated with the compatibility of other resins sometimes.In addition, being more than 20：When 1, I.e. relative to into key compound 1, when raw material polyphenylene oxide resin is more than 20, thermostability is deteriorated sometimes.
As can the present invention polynary phenylene ether novolac resin synthesis used in solvent, can enumerate Toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), Ketohexamethylene, Ketocyclopentane, butanone etc., but not limited to this, can be used alone can also And with two or more.As the solvent that can be used together, in addition to above-mentioned each solvent, methanol, ethanol, isopropyl can also be enumerated The alcohols such as alcohol, butanol；The ketones such as acetone；Ethyl acetate, butyl acetate, carbitol acetate, propylene glycol methyl ether acetate etc. Esters；The ethers such as tetrahydrofuran, dioxane；N-Methyl pyrrolidone, N,N-dimethylformamide, N, N- dimethyl second Nitrogen-containing solvents such as amide etc..Relative to raw material polyphenylene oxide resin and 100 weight portion of total amount into key compound, the use of solvent Amount is usually 5～500 weight portions, is preferably the scope of 10～400 weight portions.
As catalyst, acidic catalyst is substantially preferably used.When being benzyl halide into key compound, even if without urging Agent successfully can also be reacted, and from from the viewpoint of easy purification afterwards, preferably use without catalyst or hardly.Using urging During agent, as the concrete example of acidic catalyst, the inorganic acids such as hydrochloric acid, sulphuric acid, phosphoric acid can be enumerated；Oxalic acid, toluenesulfonic acid, The organic acids such as acetic acid；The heteropoly acids such as wolframic acid；Other displays such as active hargil, mineral acid, stannic chloride, zinc chloride, iron chloride are sour Property organic and inorganic Barbiturates etc. be generally used for acidic catalyst of novolac resin manufacture etc..These catalyst are not limited to The above-mentioned material enumerated, can be used alone and and can also use two or more.The usage amount of catalyst is relative to raw material polyphenylene oxide tree Fat is usually 0.005～2.0 times mole, is preferably 0.01～1.1 times mole of scope, or relative to raw material polyphenylene oxide resin 100g is preferably 0.1～50g, more preferably 0.3～20g.Reaction when catalytic amount is few carries out slack-off.Additionally, produce needing height Reaction, reaction under temperature can not proceed to the problem such as last, thus not preferred.In addition, when catalytic amount is excessive, in neutralization, pure Sometimes a large amount of labours are expended in the post processings such as change.
It should be noted that when corrosive gas is generated due to reaction, preferably by suction, or send into the inertia such as nitrogen Gas and from system discharge.
So obtained polynary phenylene ether novolac resin by the formula represented with following formula (A), below Illustrate the concrete example of its representative structure formula.
In resulting polynary phenylene ether novolac resin, by the polyphenylene oxide resin of the exemplary record in following B Benzene skeleton connected by the linking group of exemplary record in following A, above-mentioned linking group is by the same of polyphenylene oxide resin Benzene skeleton in one molecule is connected to each other, or will connect between the benzene skeleton of plural polyphenylene oxide resin molecule.
And, the part-structure around linking group for example forms structure as following formula (A).It should be noted that Following benzene skeletons represent the benzene skeleton in polyphenylene oxide resin molecule.
(in above-mentioned formula, P represents the residue of polyphenylene oxide resin, and X represents the linking group represented by following formula (1), and R is represented Hydrogen atom or carbon number are 1～3 alkyl, and * represents that hydrogen atom or above-mentioned X, n represent 1～2 integer.)
Here, the residue of above-mentioned polyphenylene oxide resin can be further via X at another benzene skeleton and polyphenylene oxide resin Benzene skeleton connection in molecule.
A：
(in formula, * parts are bonded with the benzene skeleton of polyphenylene oxide resin.)
B：
(n represents repetitives, represents 0～50 integer.)
(n represents repetitives, represents 0～50 integer.)
Resin-like (or powder body), solvable of the polynary phenylene ether novolac resin of the so obtained present invention for brown In organic solvent and it is also used as the resin operated by varnish.
The hydroxyl equivalent of the polynary phenylene ether novolac resin of the so obtained present invention preferably 400～6000, Particularly preferably 500～5000.
As weight average molecular weight, preferably 600～50000, particularly preferably 700～25000.
The present invention polynary phenylene ether novolac resin can be directly used as thermoplastic (or its raw material) or Mix to improve characteristic or the raw material as epoxy resin or its firming agent with thermoplastic.
Hereinafter, the composition epoxy resin to the present invention containing polynary phenylene ether novolac resin of the invention (being also referred to as hardening resin composition below) is described.In the hardening resin composition of the present invention, epoxy resin is made Use for neccessary composition.
For the hardening resin composition of the present invention, it is the group using epoxy resin-firming agent as neccessary composition Compound, it is necessary to containing polynary phenylene ether novolac resin as epoxy resin firming agent.In addition, as needed containing solid Change accelerator.
As the concrete example of the epoxy resin that can be used in the hardening resin composition of the present invention, phenol can be enumerated Novolac type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, tritan. type epoxy resin, phenol aralkyl Type epoxy resin etc..Specifically, can enumerate bisphenol-A, bisphenol S, thiodiphenol, bisphenol fluorene, terpene diphenol, 4,4 '-biphenyl Phenol, 2,2 '-xenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-biphenyl] -4,4 '-glycol, hydroquinone, resorcinol, naphthalene glycol, three (phenol, alkyl substituted phenol, naphthols, alkyl replace for (4- hydroxyphenyl) methane, 1,1,2,2- tetra- (4- hydroxyphenyl) ethane, phenols Naphthols, dihydroxy benzenes, dihydroxy naphthlene etc.) with formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, salicylaldhyde, to hydroxyl 1-Phenylethanone., o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 '-bis- (chloromethyls) -1,1 '-biphenyl, 4,4 '-bis- (methoxies Ylmethyl) -1,1 '-biphenyl, double (chloromethyl) benzene of 1,4-, double (methoxy) benzene of 1,4- etc. condensation polymer and theirs is modified Thing；The halogenated bisphenol class such as tetrabromobisphenol A, by derived from alcohols glycidyl ether compound, alicyclic epoxy resin, glycidyl Amine epoxy resin, glycidyl esters based epoxy resin etc.；Silsesquioxane based epoxy resin (chain, ring-type, scalariform or There is in the siloxane structure of wherein at least mixed structure of more than two kinds the ring of glycidyl and/or 7-oxa-bicyclo[4.1.0 structure Oxygen tree fat) etc. solid-state or liquid-state epoxy resin, but not limited to this.
As the firming agent that the hardening resin composition of the present invention contains, except the polynary phenylene ether of the above-mentioned present invention Other firming agent are can be used together beyond novolac resin.And with the case of, can be with the polynary sub- benzene of the invention described above Base ether novolac resin is used with the mode of the curing agent composition of other firming agent.And with the case of, it is of the invention More than the shared ratio in whole composition epoxy resins of polynary polyphenylene oxide novolac resin preferably 30 weight %, especially It is more than preferably 40 weight %.
As the firming agent that can be used together, such as phenol resin, phenolic compound, aminated compoundss, anhydrides can be enumerated Compound, amides compound, carboxylic acid compound etc..
It is as the concrete example of the firming agent that can be used, as described below.
Phenol resin, phenolic compounds can be enumerated：Bisphenol-A, Bisphenol F, bisphenol S, bisphenol fluorene, terpene diphenol, 4,4 '-xenol, 2,2 '-xenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-biphenyl] -4,4 '-glycol, hydroquinone, resorcinol, naphthalene glycol, three (4- Hydroxyphenyl) methane, 1,1,2,2- tetra- (4- hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline Phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, hydroxy benzaldehyde, salicylaldhyde, para hydroxybenzene Ethyl ketone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 '-bis- (chloromethyls) -1,1 '-biphenyl, 4,4 '-bis- (methoxyl groups Methyl) -1,1 '-biphenyl, 1,4 '-bis- (chloromethyl) benzene, 1,4 '-bis- (methoxy) benzene etc. condensation polymer and theirs is modified Thing；The halogenated bisphenol class such as tetrabromobisphenol A；The condensation substance of terpenes and phenols；Deng polyatomic phenol, but not limited to this.They can be single Solely use can also use two or more.
As preferred phenol resin, from from the aspect of dielectric constant, phenol aralkyl resin can be enumerated and (there are aromatic series The resin of alkylen structures), at least one structure being particularly preferably characterized by phenol, naphthols, cresol and It is that at least one resin in benzene structure, biphenyl structural, naphthalene structure (specifically can be with as the alkylene base portion of its connecting portion Enumerate xylok, naphthols xylok, phenol biphenylene novolac resin, cresol-biphenylene novolac resin, phenol- Naphthol novolak varnish gum etc.).
Aminated compoundss, amides compound can be enumerated：Diaminodiphenyl-methane, diethylenetriamines, Sanya second Urotropine, DADPS, isophorone diamine, dicyandiamide, the polyamide synthesized by linolenic dimer and ethylenediamine The nitrogen-containing compounds such as resin, but not limited to this.These can be used alone can also use it is two or more.
Anhydrides compound, carboxylic acid compound can be enumerated：Phthalic anhydride, trimellitic anhydride, Pyromellitic Acid Acid anhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, bicyclic [2.2.1] heptane -2,3- dioctyl phthalate The anhydride such as acid anhydride, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, hexamethylene -1,3,4- tricarboxylic acid -3,4- acid anhydrides；By various The carboxylic acid resin that the additive reaction of alcohol, carbinol-modified polysiloxanes and above-mentioned anhydride is obtained, but not limited to this.These can be independent It is two or more using using.
As the firming agent that other can be used together, imidazoles, trifluoroboranes-amine complex, the change of guanidine derivatives can be enumerated Compound etc., but not limited to this.These can be used alone can also use it is two or more.
In the hardening resin composition of the present invention, the usage amount of firming agent is with the epoxy radicals relative to whole epoxy resin Its functional group (hydroxyl) of 1 equivalent is preferably 0.7～1.2 equivalent when gauge.Relative to 1 equivalent of epoxy radicals be less than 0.7 equivalent when, Or during more than 1.2 equivalent, solidify not exclusively sometimes and cannot get good solidification physical property.
In the hardening resin composition of the present invention, together with firming agent and curing accelerator can be used.As can make The concrete example of curing accelerator, can enumerate the imidazoles such as 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole Class；The tertiary amines such as 2- (dimethylamino methyl) phenol, 1,8- diazabicyclos (5.4.0) hendecene -7；The phosphines such as triphenylphosphine； The quaternary ammonium salts such as 4-butyl ammonium, triisopropyl methyl ammonium salt, trimethyldecylammonium ammonium salt, cetyltrimethyl ammonium salt；Triphenyl BenzylSalt, triphenyl ethylSalt, the tetrabutylThe seasons such as saltSalt.(counter ion counterionsl gegenions of quaternary salt be halogen, organic acid from Son, hydroxide ion etc., although do not specify, but particularly preferably organic acid ion, hydroxide ion.) can enumerate it is pungent Metallic compounds such as sour stannum etc..In the case of using curing accelerator, relative to 100 weight portion of epoxy resin, make as needed With 0.01～5.0 weight portion.
Composition can also be given as anti-flammability containing phosphorus-containing compound in the hardening resin composition of the present invention.As Phosphorus-containing compound, can both be response type phosphorus-containing compound can also be addition type phosphorus-containing compound.As phosphorous chemical combination The concrete example of thing, can enumerate trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid first Double (two (xylyl) phosphoric acid of phenylester diphenyl, tricresyl phosphate base ester -2,6- two (xylyl) ester, 1,3- phenylenes Ester), the phosphoric acid ester such as 1,4- phenylenes double (two (xylyl) phosphate ester), 4,4 '-biphenyl (two (xylyl) phosphate ester)； Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of 9,10- dihydro-9-oxies, 10- (2,5- dihydroxy phenyls) -10H-9- oxa- -10- phosphas The phosphines such as phenanthrene -10- oxides；Make epoxy resin and phosphorous epoxide obtained from the reactive with active hydrogen of above-mentioned phosphine, red Phosphorus etc., but preferably phosphoric acid esters, phosphine or phosphorous epoxide, double (two (xylyl) phosphorus of particularly preferred 1,3- phenylenes Acid esters), 1,4- phenylenes double (two (xylyl) phosphate ester), 4,4'- biphenyl (two (xylyl) phosphate ester) or phosphorous ring Oxygen compound.The content of phosphorus-containing compound is preferably phosphorus-containing compound/whole epoxy resin=0.1～0.6 (weight ratio).0.1 When following, anti-flammability is not enough sometimes, and when more than 0.6, the hygroscopicity of solidfied material, dielectric property decline sometimes.
Additionally, antioxidant can be added as needed in the hardening resin composition of the present invention.As can use Antioxidant, phenols, sulfur-bearing, phosphorous antioxidant can be enumerated.Antioxidant can be used alone or be applied in combination two kinds More than.The usage amount of antioxidant is usual relative to 100 weight portion of resinous principle in the hardening resin composition of the present invention For 0.008～1 weight portion, it is preferably 0.01～0.5 weight portion.
As the concrete example of phenol antioxidant, can illustrate：DBPC 2,6 ditertiary butyl p cresol, Butylated hydroxy benzene first Ether, 2,6- di-t-butyl paraethyl phenols, β-(3,5- di-tert-butyl-hydroxy phenyls) propanoic acid stearyl ester, 3- (bis- uncles of 3,5- Butyl -4- hydroxy phenyls) the different monooctyl ester of propanoic acid, double (just pungent the sulfenyl) -6- (4- hydroxyl -3,5- di-tert-butyl amidos) -1 of 2,4-, The unitary phenols such as double [(pungent sulfenyl) the methyl]-orthoresols of 3,5- triazines, 2,4-；2,2 '-di-2-ethylhexylphosphine oxide (4- methyl-6-tert butyl Phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-thiobiss (3 methy 6 tert butyl phenol), 4, Double [the 3- (the 3- tert-butyl group -5- methyl -4- hydroxy phenyls) third of 4 '-butylidene-bis(3-methyl-6-t-butyl phenol), triethylene glycol Acid esters], 1,6-HD-bis- [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], N, N '-hexamethylene bis (3,5- bis- Tertiary butyl-4-hydroxy hydrocinnamamide), 2,2- thiodiethylenes double [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], Double [1,1- dimethyl -2- { the β-(3- tertiary butyl-4-hydroxy -5- of diethyl 3,5-di-t-butyl-4-hydroxybenzyl phosphonate, 3,9- Aminomethyl phenyl) propionyloxy ethyl] 2,4,8,10- tetra- oxaspiros [5.5] hendecanes, double (3,5- di-t-butyl -4- hydroxyl benzyls Base sulfonic acid) bisphenols such as calcium；1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, 1,3,5- trimethyls - 2,4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, four-[methylene -3- (3 ', 5 '-di-t-butyl -4 '-hydroxyphenyl) third Acid esters] methane, double [3,3 '-bis--(4 '-hydroxyl -3 '-tert-butyl-phenyl) butanoic acid] diol esters, three (3,5- di-t-butyl -4- hydroxyls Base benzyl) isocyanuric acid ester, 1,3,5- tri- (3 ', 5 '-di-t-butyl -4 '-hydroxybenzyl) guanamine, 4,6- (1H, 3H, 5H) The polymer electrolyte phenols such as triketone, tocopherol.
As the concrete example of sulphur-containing antioxidant, can illustrate：3,3 '-dilauryl thiodipropionate, 3,3 '-thio two Two myristin of propanoic acid, 3,3 '-distearylthiodi-propionate etc..
As the concrete example of phosphorous antioxidant, can illustrate：Triphenyl phosphite, diphenyl phosphite isodecyl Ester, phenyl ester diiso decyl ester, phosphorous acid three (nonyl phenyl) ester, phosphorous acid diiso decyl ester pentaerythritol ester, Asia Tricresyl phosphate (2,4- di-tert-butyl-phenyls) ester, four base of phosphorous acid ring-type neopentane double (octadecyl) ester, phosphorous acid ring-types new penta Double (2,4- di-tert-butyl-phenyls) esters of four base of alkane, four base of phosphorous acid ring-type neopentane are double (2,4- di-t-butyl -4- aminomethyl phenyls) The phosphorous acid esters such as ester, double [the 2- tert-butyl group -6- methyl -4- { 2- (octadecane epoxide carbonyl) ethyl } phenyl] H-Phosphonates； Miscellaneous -10- phospho hetero phenanthrenes -10- the oxides of 9,10- dihydro-9-oxies, 10- (3,5- di-tert-butyl-4-hydroxyl benzyls) -9,10- dihydros - The oxygen such as 9- oxa- -10- phospho hetero phenanthrene -10- oxides, the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 10- decyloxy -9,10- dihydro-9-oxies Miscellaneous phospho hetero phenanthrene is oxide-based etc..
These antioxidants individually can be used, it is also possible to combine two or more being used in combination.Particularly, it is excellent in the present invention Select phosphorous antioxidant.
Additionally, light stabilizer can be added as needed in the hardening resin composition of the present invention.
As light stabilizer, preferred hindered amine light stabilizer, especially HALS etc..It is not particularly limited as HALS, As typical case, can enumerate：Dibutyl amine 1,3,5- triazines N, N '-bis- (2,2,6,6- tetramethyl -4- piperidyl -1,6- The condensation polymer of hexamethylene diamine and N- (2,2,6,6- tetramethyl -4- piperidyls) butylamine, dimethyl succinate -1- (2- ethoxys) -4- Hydroxyl -2,2,6,6- tetramethyl piperidine condensation polymers, poly- [{ 6- (1,1,3,3- tetramethyl butyls) amino -1,3,5- triazine -2,4- Diyl } { (2,2,6,6- tetramethyl -4- piperidyls) imino group } hexa-methylene { (2,2,6,6- tetramethyl -4- piperidyls) imido Base }], [[3,5- double (1,1- dimethyl ethyls) -4- hydroxy phenyls] methyl] butylmalonic acid it is double (1,2,2,6,6- pentamethyls - 4- piperidyls) ester, double (2,2,6,6- tetramethyl -4- piperidyls) ester of decanedioic acid, the double (1,2,2,6,6- pentamethyl -4- of decanedioic acid Piperidyl) ester, decanedioic acid double (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) ester, 2- (3,5- di-t-butyl -4- hydroxyls Benzyl) double (1,2,2,6,6- pentamethyl -4- piperidyls) esters of -2- n-butylmalonic acids etc..HALS only using one kind also can may be used With and with two or more.
Additionally, resin glue can also be coordinated in the hardening resin composition of the present invention as needed.As bonding Agent resin, can enumerate：Butyral resinoid, acetal-based resin, acrylic resin, epoxy-nylon-based resin, NBR- phenols Resin, epoxy-NBR resinoids, polyamide-based resin, polyimide based resin, polysiloxanes resinoid etc., but not limited to this. The use level of resin glue does not preferably damage the anti-flammability of solidfied material, the scope of thermostability, relative to 100 weight of resinous principle Amount part generally according to need using 0.05～50 weight portion, be preferably 0.05～20 weight portion.
Inorganic filler can be added as needed in the hardening resin composition of the present invention.As inorganic filler, Can enumerate：Crystalline silica, fused silica, aluminium oxide, zircon, calcium silicates, Calcium Carbonate, carborundum, silicon nitride, nitrogen Change the powder body of boron, zirconium oxide, forsterite, steatite, spinelle, titanium dioxide, Talcum etc. or their spheroidizations are obtained Pearl etc., but not limited to this.They can be used alone can also use it is two or more.The content of these inorganic fillers can be with Using the amount that 0～95 weight % is accounted in the hardening resin composition of the present invention.Additionally, the curable resin combination of the present invention The releasing agents such as silane coupler, stearic acid, Palmic acid, zinc stearate, calcium stearate can be added in thing；Surfactant, dye The various compounding ingredients such as material, pigment, UV absorbent, various thermosetting resins.
The hardening resin composition of the present invention can be by each composition be obtained by uniformly mixingg.The curable of the present invention Resin combination can be readily derived its solidfied material by the method same with previously known method.For example make as needed With the solidification by the polyphenylene oxide novolac resin and epoxy resin of the present invention and as needed such as extruder, kneader, roller Accelerator, phosphorus-containing compound, resin glue, inorganic filling material and compounding ingredient are fully mixed to uniformly, so as to be solidified Property resin combination, will hardening resin composition perfusion, (need not melt during liquid) after melting carry out cast molding or Person carries out molding using transfer molding machine etc., then heats 2～10 hours at 80～200 DEG C, it is hereby achieved that the present invention Solidfied material.
In addition, by the present invention hardening resin composition be dissolved in as needed toluene, dimethylbenzene, acetone, butanone, Methyl iso-butyl ketone (MIBK), dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone equal solvent and obtain curable resin group Compound varnish so as to be infiltrated up in the base materials such as glass fibre, carbon fiber, polyester fiber, Fypro, alumina fibre, paper, And be thermally dried, resulting prepreg is carried out it is hot-forming, it is hereby achieved that the curable resin group of the present invention The solidfied material of compound A.Solvent now is using usual in the hardening resin composition of the present invention with the mixture of the solvent Account for 10～70 weight %, be preferably the amount of 15～70 weight %.In addition, if being fluid composition, then directly can also utilize For example RTM modes obtain the epoxy resin cured product containing carbon fiber.
Alternatively, it is also possible to the hardening resin composition of the present invention to be used as the modifying agent of membranous type compositionss.Specifically, Can be used for improving the situation of the flexibility of (B) in the stage etc..The resin combination of this membranous type can be obtained as follows：By the present invention Hardening resin composition make above-mentioned hardening resin composition varnish and coat on stripping film, remove under heating molten Agent, then carry out (B) it is staged, thus obtain the adhesive of lamellar.The Web-form adhesive is can serve as in multilager base plate etc. Interlayer insulating film.
The hardening resin composition of the present invention can enumerate the normal usage using epoxy resin, can enumerate such as glue Stick, coating, smearss, moulding material (including sheet material, film, FRP etc.), insulant (include printed base plate, coating electric wire Deng), sealant and to additive of addition etc. in other resins etc..As adhesive, can enumerate building use, it is for building, The adhesive of automobile use, routine office work use, therapeutic medical adhesive and electronic material.Among these, as electronic material Adhesive, can enumerate the quasiconductors such as the interlaminated adhesive of the multilager base plates such as increasing layer substrate, chip cement, bottom filling With installation glue such as adhesive, BGA enhancing bottom fillings, anisotropic conductive film (ACF), anisotropic conductive cream (ACP) Stick etc..
As sealant, substrate, capacitor, transistor, diode, light emitting diode, IC, LSI etc. can be enumerated Embedding, dipping, transmission die sealing；The embedding sealing of COB, COF, TAB of IC, LSI class etc.；The bottom of flip-chip etc. Filler；Sealing (including enhancing bottom filling) and base plate for packaging when the IC package body such as QFP, BGA, CSP class is installed etc..Separately Outward, network substrate, module substrate etc. are also suitable for and require functional substrate purposes.
Embodiment
Then, more specific description is carried out to the present invention by embodiment, hereinafter unless otherwise specified, part refers to Weight portion.It should be noted that the invention is not restricted to these embodiments.
Hereinafter, to embodiment used in various analysis methods be described.
Epoxide equivalent：According to JIS K 7236 (ISO3001)
ICI melt viscosities：According to JIS K 7117-2 (ISO3219)
Softening point：According to JIS K 7234
Total chlorine：According to JIS K 7243-3 (ISO21672-3)
GPC：
Post (Shodex KF-603, KF-602.5, KF-602, KF-601 × 2)
Connection eluent is tetrahydrofuran
Flow velocity is 0.5ml/ minutes
Column temperature is 40 DEG C
Detection：RI (differential refraction detector)
Hereinafter, the present invention is specifically described by embodiment, comparative example.
(embodiment 1)
In possessing blender, reflux cooling pipe, the flask of agitating device, implementing to add polyphenyl while nitrogen is purged 175 parts of ether resin (Mn=2066, Mw=3553, Mz=5951 in SABIC MX90-100, GPC figures), terephthalyl alcohol (east Capital is melted into reagent processed) 9.6 parts, 300 parts of toluene (pure chemistry processed reagent), (Tokyo is melted into make and tries p-methyl benzenesulfonic acid monohydrate Agent) 2 parts, react 2 hours at 100 DEG C, afterwards, become reflux state at 110～120 DEG C, and keep the state to carry out 7 hours Reaction.
After reaction terminates, 200 parts of methyl iso-butyl ketone (MIBK) is added, washing is repeated, after confirming that water layer becomes neutrality, used Rotary evaporator is distilled off solvent from oil reservoir under reduced pressure, resulting in the polynary phenylene ether novolaks of the present invention 179 parts of resin (P-1).(it should be noted that as Mn=2091 in the GPC figures of the polyphenylene oxide resin of raw material, Mw=4215, Mz=7774.)
(embodiment 2)
In possessing blender, reflux cooling pipe, the flask of agitating device, implementing to add polyphenyl while nitrogen is purged 75 parts of ether resin (SABIC MX90-100), 5 parts of terephthalyl alcohol (Tokyo is melted into reagent processed), toluene (pure chemistry system examination Agent) 130 parts, 1 part of p-methyl benzenesulfonic acid monohydrate (Tokyo is melted into reagent processed), in 100 DEG C of reactions 2 hours, afterwards, 110～ Become reflux state at 120 DEG C, and keep the state to carry out 10 hours reacting.
After reaction terminates, 100 parts of methyl iso-butyl ketone (MIBK) is added, washing is repeated, after confirming that water layer becomes neutrality, used Rotary evaporator slowly removes solvent from oil reservoir under reduced pressure, confirms no longer outflow water, adds methyl iso-butyl ketone (MIBK), is adjusted to Resin concentration 50%.Resulting in 143 parts of the polynary phenylene ether novolac resin varnish (V-1) of the present invention.The figure of GPC Middle Mn=2111, Mw=4345, Mz=7932.
(embodiment 3)
In possessing blender, reflux cooling pipe, the flask of agitating device, implementing to add polyphenyl while nitrogen is purged 87.5 parts of ether resin (SABIC MX90-100), 4.8 parts of terephthalyl alcohol (Tokyo is melted into reagent processed), methyl iso-butyl ketone (MIBK) are (pure Positizing length of schooling reagent) 138 parts, 1 part of p-methyl benzenesulfonic acid monohydrate (Tokyo is melted into reagent processed), in 100 DEG C of reactions 2 hours, it Afterwards, become reflux state at 110～120 DEG C, and keep the state to carry out 7 hours reacting.
After reaction terminates, methyl iso-butyl ketone (MIBK) 100 is added, washing is repeated, after confirming that water layer becomes neutrality, used Rotary evaporator slowly removes solvent from oil reservoir under reduced pressure, confirms no longer outflow water, adds methyl iso-butyl ketone (MIBK), is adjusted to Resin concentration 60%.
50 parts of the polynary phenylene ether novolac resin varnish (V-2) of the present invention obtained by adding, phenol Asia biphenyl 70 parts of base novolaks (Japanese chemical medicine KAYAHARD GPH-65), after dissolving, are distilled using rotary evaporator under reduced pressure and are removed Solvent is gone, so as to obtain the curing agent composition of the polynary phenylene ether novolac resin containing 30% present invention (H-1).Softening point is 121 DEG C.
(embodiment 4)
Except in embodiment 3 by 70 parts of phenol biphenylene novolaks (Japanese chemical medicine KAYAHARD GPH-65) Become 30 parts in addition, similarly operated, obtain the curing agent composition (H-2) of the present invention.
(embodiment 5)
Except in embodiment 3 by 70 parts of phenol biphenylene novolaks (Japanese chemical medicine KAYAHARD GPH-65) Become 20 parts in addition, similarly operated, obtain the polynary phenylene ether novolac resin containing 60% present invention Curing agent composition (H-3).Softening point is 130 DEG C.
(embodiment 6)
In possessing blender, reflux cooling pipe, the flask of agitating device, implementing to add polyphenyl while nitrogen is purged 100 parts of ether resin (Mn=2960, Mw=6863, Mz=11851 in SABIC SA120-100, GPC measure), terephthalyl alcohol 140 parts of 10 parts of (Tokyo be melted into processed reagent), toluene (pure chemistry processed reagent), (Tokyo is melted into and makes p-methyl benzenesulfonic acid monohydrate Reagent) 2.0 parts, react 2 hours at 100 DEG C, afterwards, become reflux state at 110～120 DEG C, and keep the state response 7 Hour.
After reaction terminates, butanone 100 is added, slowly instill in the container equipped with 1000 parts of methanol, carry out reprecipitation. After resulting toner is filtered, with 100 parts of methanol：Water=1：After 1 is cleaned, 5 times are carried out with 100 parts of water clearly Wash.Thus, 89 parts of the polynary phenylene ether novolac resin (P-3) of the present invention has been obtained.Mn=3683, Mw=in GPC figures 7356th, Mz=11860.In addition, relative to 30 parts of resulting (P-3), using 50 parts of KAYAHARD GPH-6520 parts, toluene, After being mixed, solvent is distilled off under reduced pressure using rotary evaporator, so as to obtain curing agent composition (H-4).
(comparative example 1)
Add 30 parts of polyphenylene oxide resin (SABIC MX90-100), phenol biphenylene novolaks (Japanese chemical medicine system KAYAHARD GPH-65) 70 parts, after being dissolved in methyl iso-butyl ketone (MIBK), solvent is distilled off under reduced pressure using rotary evaporator Class, so as to obtain the curing agent composition for comparing (H ' -1).
(comparative example 2)
Add 30 parts of polyphenylene oxide resin (SABIC MX90-100), phenol biphenylene novolaks (Japanese chemical medicine system KAYAHARD GPH-65) 20 parts, after being dissolved in methyl iso-butyl ketone (MIBK), solvent is distilled off under reduced pressure using rotary evaporator Class, so as to obtain the curing agent composition for comparing (H ' -2).
Embodiment 7～8 and comparative example 3
＜ K dielectric loss tangent test ＞
Ratio (weight portion) with table 1 coordinates curing agent composition and epoxy resin for above obtaining etc., using mixing Roller is uniformly mixed and is kneaded, and has obtained encapsulating epoxy resin composition.Using blender by the composition epoxy resin Crush, then pelletize is carried out using comminutor.Transfer molding (175 DEG C × 60 is carried out to the composition epoxy resin after the pelletize Second), then solidified under conditions of+180 DEG C × 6 hours 160 DEG C × 2 hours after demoulding, used so as to obtain evaluating Test film.
It should be noted that the physical property of solidfied material is measured according to following main points.
K dielectric loss angle tangent：Cavity resonator method
Cavity resonator 1GHz is developed using equipment Northeast electrical applications
Reference Teflon (registered trade mark)
[table 1]
EP-1：Biphenyl phenol aralkyl type epoxy resin (NC3000)
GPH-65：Biphenyl phenol aralkyl type phenol resin
TPP：Triphenylphosphine
Embodiment 9 and comparative example 4
＜ Dielectric Property Testing heat-resistance test ＞
Ratio (weight portion) with table 2 coordinates curing agent composition and epoxy resin for above obtaining etc., using mixing Roller is uniformly mixed and is kneaded, and has obtained encapsulating epoxy resin composition.Using blender by the composition epoxy resin Crush, then pelletize is carried out using comminutor.Transfer molding (175 DEG C × 60 is carried out to the composition epoxy resin after the pelletize Second), then solidified under conditions of+180 DEG C × 6 hours 160 DEG C × 2 hours after demoulding, used so as to obtain evaluating Test film.
It should be noted that the physical property of solidfied material is measured according to following main points.
K dielectric loss angle tangent：Cavity resonator method
Cavity resonator 1GHz is developed using equipment Northeast electrical applications
Reference Teflon (registered trade mark)
Thermostability (TMA)：It is measured according to JIS K 7244.
[table 2]
Embodiment 10 and comparative example 5
＜ heat-resistance test Dielectric Property Testings ＞
Ratio (weight portion) with table 3 coordinates curing agent composition and epoxy resin for above obtaining etc., using mixing Roller is uniformly mixed and is kneaded, and has obtained encapsulating epoxy resin composition.Using blender by the composition epoxy resin Crush, then pelletize is carried out using comminutor.Transfer molding (175 DEG C × 60 is carried out to the composition epoxy resin after the pelletize Second), then solidified under conditions of+180 DEG C × 6 hours 160 DEG C × 2 hours after demoulding, used so as to obtain evaluating Test film.
It should be noted that the physical property of solidfied material is measured according to following main points.
K dielectric loss angle tangent：Cavity resonator method
Cavity resonator 1GHz is developed using equipment Northeast electrical applications
Reference Teflon (registered trade mark)
Thermostability (DMA)
Measurement of Dynamic Viscoelasticity device：TA-instruments、DMA-2980
Temperature of the measurement scope：- 30～280 DEG C
Cooling rate：2 DEG C/min
Test chip size：(about 800 μm of thickness) is used after cutting into 5mm × 50mm
Tg：Using the summit of Tan- δ as Tg
Thermostability (TMA)：It is measured according to JIS K 7244.
[table 3]
By result above it has been confirmed that the hardening resin composition of the present invention is used as firming agent (compositionss), with use Have a case that the H ' -1 of similar structures, H ' -2 are compared, hence it is evident that more excellent in terms of thermostability, and with using other firming agent Situation compare, dielectric constant, dielectric loss angle tangent are also better, with excellent dielectric property.
The present invention is described in detail with reference to ad hoc fashion, but in the situation without departing from the spirit and scope of the present invention Under can carry out various change and amendment, this is obvious to those skilled in the art.
It should be noted that the application is based in Japanese patent application (Japanese Patent Application filed in 6 days November in 2012 2012-244309), and by quoting entire contents are incorporated herein.In addition, cited herein all with reference to as whole Body is incorporated herein.
Industrial applicability
The polyphenylene oxide novolac resin of the present invention is useful as the firming agent etc. of epoxy resin, containing the polyphenylene oxide phenolic aldehyde Varnish gum as firming agent composition epoxy resin with electrical and electronic parts insulant and plywood (printed wiring Plate, increasing layer substrate etc.), it is the various composites headed by CFRP, adhesive, useful in coating etc..

Claims (4)

1. a kind of polynary phenylene ether novolac resin, its pass through by molecular weight 400～8000 (weight average molecular weight, by polyphenyl Ethylene converts) polyphenylene oxide resin connected by organic group and obtained, and represented with following formula (A),
In above-mentioned formula, P represents the residue of polyphenylene oxide resin, X be organic group and in representing by following formula (1) at least any one The linking group of expression, R represent the alkyl that hydrogen atom or carbon number are 1～3, and * represents that hydrogen atom or above-mentioned X, n represent 1～2 Integer,
Formula（1）In, * parts are bonded with the benzene skeleton of polyphenylene oxide resin.
2. polynary phenylene ether novolac resin as claimed in claim 1, wherein, polyphenylene oxide resin is biphenyl phenols or double The oxypolymer of phenols and Phenol compounds.
3. a kind of composition epoxy resin, which contains the polynary phenylene ether novolaks described at least one claim 1 or 2 Resin.
4. a kind of solidfied material, which is obtained by making the epoxy resin composition described in claim 3.
CN201380058014.2A 2012-11-06 2013-11-05 Polyvalent phenylene ether novolac resin, epoxy resin composition, and cured product thereof Expired - Fee Related CN104781307B (en)

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CN104781307A (en) 2015-07-15
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WO2014073536A1 (en) 2014-05-15
KR102047681B1 (en) 2019-11-22
JPWO2014073536A1 (en) 2016-09-08
KR20150082181A (en) 2015-07-15

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